ELECTRON CONFIGURATION AND THE PERIODIC TABLE

ELECTRON CONFIGURATION AND THE PERIODIC TABLE The electrons in an atom fill from the lowest to the highest orbitals. The knowledge of the location of the orbitals on the periodic table can greatly help the writing of electron configurations for large atoms. 15

For A Groups (Representative Elements): For B Groups (Transition Elements) (s and p blocks) n = period number d blocks: n = period number 1 f blocks: n = period number 2 The electronic configuration of an element can now be given if the position in the Periodic Table is known: 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 10 4p 6 5s 2 1s 2 2s 2 2p 6 3s 2 3p 3 or [Kr] 5s 2 or [Ne] 3s 2 3p 3 (2 outermost shell electrons) (5 outermost shell electrons) 1s 2 2s 2 2p 6 3s 2 3p 6 4s 2 3d 6 or [Ar] 4s 2 3d 6 (2 outermost shell electrons) 16

Group VIIIA elements (Noble Gases) have a stable outermost shell electron configuration: Element Orbital Notation Electron Configuration He 1s # of Outermost Shell Electrons 1s 2 2 Ne Ar Kr Xe Rn 2s 2p 3s 3p 4s 4p 5s 52p 6s 6p 2s 2 2p 6 8 3s 2 3p 6 8 4s 2 4p 6 8 5s 2 5p 6 8 6s 2 6p 6 8 The electron configuration of ns 2 np 6 (or ns 2 ) is referred to as a noble gas core Chemical Properties of elements are determined by the outermost shell electrons (electrons in highest energy level); these electrons are involved in bonding. VALENCE ELECTRONS: Valence electrons are those outside the noble gas core For transition elements, the s and p electrons of the outermost shell (highest energy level) ( d electrons are not valence electrons) NOTE: Most transition elements have 2 valence electrons Reason: They fill d or f orbitals which are not part of the outer most shell Exceptions: Transition elements with irregular electronic configurations: Cr, Cu, etc. 17

MAGNETIC PROPERTIES OF ATOMS Every electron acts like a small magnet Magnetic attractions from 2 electrons with opposite spin cancel each other It follows: An atom with paired electrons has no magnetism. An atom with unpaired electrons (excess of one spin) exhibits magnetism. An element with atoms that exhibit magnetism is attracted to a strong magnet DIAMAGNETIC ELEMENTS PARAMAGNETIC ELEMENTS Are not attracted by a magnetic field Sometimes even repelled by a magnetic field Atoms contain paired electrons only Are weakly attracted by a magnetic field Atoms contain unpaired electrons Hg [Xe] 6s 2 4f 14 5d 10 Na [Ne] 3s 1 C [He] 2s 2 2p 2 FERROMAGNETIC ELEMENT Are strong permanent magnetism in iron due to the alignment of many unpaired electrons Fe [Ar] 4s 3d Examples: 1. Write complete and condensed electron configuration for bromine (Z=35) and determine the number of valence electrons. 2. Write complete and condensed electron configuration for palladium (Z=46) and determine the number of valence electrons. 3. Write complete and condensed electron configuration for antimony (Z=51) and determine the number of valence electrons. 18

PERIODIC PROPERTIES Periodic properties are properties of the elements that are repeated according to a regular periodic trend. Three important periodic properties will be discussed: 1. Atomic Radius (size of the atoms) 2. Ionization Energy (I.E.) energy needed to remove the outermost electron from a neutral atom in the gaseous state to form a positive ion. 3. Electron Affinity (E.A.) energy (absorbed or released) during the process of adding an electron to a neutral atom in the gaseous state to form a negative ion The variation of these 3 Periodic Properties will be discussed : within a group (vertical trend) along a period (horizontal trend) Two important factors determine these trends: Effective Nuclear Charge increases 19

Effective Nuclear Charge Effective nuclear charge (Z eff ) is the positive charge that an electron experiences from the nucleus. Consider the electron configuration of the Na atom ( Z = 11) 1s 2 2s 2 2p 6 3s 1 +11 2e 8e 3 energy levels: 2 electrons on 1 st energy level 8 electrons on 2 nd energy level 1 electron on 3 rd energy level What is the positive charge that the outermost electron feels? 1. It is not +11, since its electrons of the 1 st and 2 nd energy level (10 electrons carry a charge equal to 10) = cancel out some of the + 11 charge of the nucleus ( shielding effect ) 2. It is not + 1, since the 10 core electrons (charge = 10) cannot completely cancel out 10 positive charges of the nucleus. Reason: The 10 core electrons are in the nucleus, but some distance away Note: The closer to the nucleus the core electrons are, the more effective they are in canceling out some of the positive charge of the nucleus (shielding effect) shielding effect of a 1 st shell electron shielding effect of a 2 nd shell electron 3. The outermost electron is attracted to the nucleus by a positive charge which is less than the actual nuclear charge (Z = +11) because of the shielding effect of the core electrons, but more than +1 Effective Nuclear Charge = Zeff = + 2.8 (in this particular case) The Nuclear Charge an outermost electron experiences is reduced by the shielding effect of other electrons (Zeff = Z Shielding Effect) Zeff = Z Shielding effect Effective Nuclear Charge Actual Nuclear Charge 20

Along a period, moving from left to right: Protons are added to the nucleus Electrons are added to the outermost shell Z increases considerably Minimal increase in shielding effect Zeff = Z Shielding effect Effective Nuclear Charge Actual Nuclear Charge Increases considerably Minimal increase Moving across a period Zeff increases (Z increases a lot, Shielding Effect increases little) Along a group, moving from up to down: Protons are added to the nucleus Electrons are added to the new shell Z increases considerably Considerable increases shielding effect Zeff = Z Shielding effect Effective Nuclear Charge Actual Nuclear Charge Increases considerably Increases considerably Moving down a group Zeff does NOT increase (Z increases a lot, Shielding Effect increases a lot) 21

ATOMIC RADIUS Values of Atomic radii are obtained from measurements of distances between the nuclei of atoms in the chemical bonds of molecular substances. Example: experimental Determination of the radius of H atom: Atomic Radius = ½ distance between nuclei distance between nuclei is determined experimentally (by X ray crystallography) Atomic Radius determined in this manner are referred to as Covalent Radii. Atoms are very small; consequently, atomic radii have very small values Values of Atomic Radii are listed on the Periodic Table (back side) and are commonly expressed in: or or Angstroms (1 A = 10 10 m) Nanometers (1 nm = 10 9 m) Picometers (1 pm = 10 12 m) H is the smallest atom: Covalent radius of H atom = 0.32 A 22

ATOMIC RADII Atomic Size Increases 23

ATOMIC RADII Note: There is little variation in atomic Size throughout a row of Transition Elements: Reason: Consider the elements completing the 3d subshell: From Sc..to.Zn [Ar] 4s 2 3d 1....to [Ar] 4s 2 3d 10 Moving along period 4 from left to right: 1 proton is added when moving from one transition element to the next ACTUAL NUCLEAR CHARGE (Z) INCREASES CONSIDERABLY Sc..Zn 1 electron is added to the 3d subshell of the 3 rd shell (an inner shell) SHIELDING EFFECT CAUSED BY ADDED ELECTRON INCREASES CONSIDERABLY Recall: Zeff = Z Shielding Effect increases increases considerably considerably Result: Zeff does not change Insignificant variation in Atomic Size for 3d block elements This trend holds true for all transition elements (d block elements) 24

IONIZATION ENERGY Ionization Energy (IE) is the energy needed to remove the outermost electron from a neutral atom in the gaseous state to form a positive ion. Ionization Energy : is commonly measured in kj/mol is also referred to as Ionization Potential (electrical energy) and can also be measured in Volts is listed on the Periodic Table (back side) Consider the removal of the outermost shell electron from sodium: Na(g) + IE 1 Na + (g) + 1 e 1s 2 2s 2 2p 6 3s 1 First Ionization 1s 2 2s 2 2p 6 [Ne] 3s 1 Energy [Ne] (11p, 11e) (11p, 10e) Consider the removal of a second electron: Na + (g) + I E 2 Na 2+ (g ) + 1 e 1s 2 2s 2 2p 6 Second Ionization 1s 2 2s 2 2p 5 [Ne] Energy [He] 2s 2 2p 5 (11p, 10e) (11p, 9e) NOTES: 1. Removal of an electron is an endothermic process (it requires energy to remove an electron) Atoms do not lose electrons; Energy is required to remove the electrons 2. All the electrons can be removed successively form an atom. The energies required at each step are known as: First Ionization Energy (IE 1 ), Second Ionization Energy (IE 2 ), Third Ionization Energy (IE 3 ). 3. In general: The Ionization Energies for a given element increase as more electrons are removed: I E 1 < I E 2 < I E 3 < I E 4 < I E 5 < I E 6 < I E 7 < I E 8 and so on. Reason: The electron is being removed from ions with increasingly larger positive charges (The larger the positive charge of the ion, the stronger the electron is attracted) 25

IONIZATION ENERGY Down a group IE decreases, due to increased atomic size (the larger the atom, the less strongly it holds its electrons in the outer shell) Across a period, IE generally increases, due to increased effective nuclear charge (the greater the nuclear charge, the stronger the atom hold its electrons in the outer shell) Some anomalies in IE trend occur in each period (e.g. in period 2, B is lower than Be and O is lower than N; similarly in period 3, Al is lower than Mg and S is lower than P). These anomalies are due to the increased stabilities of the electron shell arrangements for each atom. 26

The increase in the values of successive Ionization Energies is not gradual: Element Successive Ionization Energies (kj/mol) IE 1 IE 2 IE 3 IE 4 IE 5 IE 6 IE 7 H 1312 He 2372 5250 Li 520 7298 11,815 Be 899 1757 14,848 21,006 B 801 2427 3660 25,025 32,826 C 1086 2353 4620 6222 37,829 47,276 N 1402 2857 4578 7475 9445 53,265 O 1314 3388 5300 7469 10,989 13,326 71,333 F 1681 3374 6020 8407 11,022 15,164 17,867 NOTE: A very large jump in the I E value occurs after all the valence electrons have been removed Element Successive Ionization Energies (kj/mol) IE 1 IE 2 IE 3 IE 4 IE 5 IE 6 IE 7 H 1312 He 2372 5250 Li 520 7298 11,815 Be 899 1757 14,848 21,006 B 801 2427 3660 25,025 32,826 C 1086 2353 4620 6222 37,829 47,276 N 1402 2857 4578 7475 9445 53,265 O 1314 3388 5300 7469 10,989 13,326 71,333 F 1681 3374 6020 8407 11,022 15,164 17,867 Once the valence electrons are removed, a stable noble gas configuration is obtained. Further removal of electrons will involve electrons from a complete inner shell. For purposes of comparing the chemical behavior of different elements, usually only the First Ionization Energy (IE 1 ) is compared. 27

SUMMARY OF ATOMIC RADIUS & IONIZATION ENERGY NONMETALS HIGH IONIZATION ENERGY RELATIVELY SMALL ATOMS METALS LOW IONIZATION ENERGY RELATIVELY LARGE ATOMS Zeff decreases Ionization Energy Decreases 29

ELECTRON AFFINITY (EA) Consider the electron configuration of the Cl atom (Z = 17) 1s 2 2s 2 2p 6 3s 2 3p 5 3 energy levels: 2 electrons on the 1 st energy level 8 electron on the 2 nd energy level 7 electrons on the 3 rd energy level? +17 What is the effect (if any) of the Cl atom on an outside electron? Hypothetically, there are 3 possibilities: 1. The atom is neutral (+ 17 nuclear charge is canceled out by the 17 negative electrons) As such, the outside electron should be unaffected by the neighboring Cl atom 2. The 17 electrons of the Cl atom (charge = 17) should repel the outside electron 3. The 17 electrons of the Cl atom cancel out the positive nuclear charge of +17 only partially (shielding effect). The positively charged nucleus creates an electric field which should attract the outside electron 30

The outside electron is attracted to the Cl atom, and is accepted by the Cl atom. The addition of the electron to the Cl atom does not require energy (not endothermic) The electron is naturally attracted and releases energy (exothermic process) +17 Cl + e Cl + 349 kj/mole 1s 2 2s 2 2p 6 3s 2 3p 5 1s 2 2s 2 2p 6 3s 2 3p 6 [Ne] 3s 2 3p 5 [Ne] 3s 2 3p 6 [Ar] 31

Recall that the heat term is always written on the reactant side (Thermochemistry) Cl + e 349 kj/mole + Cl Cl + e Cl H = 349 kj/mole (exothermic) ELECTRON AFFINITY ELECTRON AFFINITY (EA) is the energy change (commonly released) for the process of adding an electron to a neutral atom in the gaseous state to form a negative ion. (it is a measure of how easily an atom accepts an electron) NOTE: 1. The majority of atoms have a high tendency to gain electrons (ex: Cl) The atoms have HIGH EA s HIGH EA means LARGE NEGATIVE EA Large Amount of Energy given off when an electron is gained willingly by the neutral atom (stable ion formed) (addition of electron is exothermic) 2. Relatively few atoms resist the addition of an electron(ex:noble Gases and some metals) They have LOW EA s LOW EA means Zero or Positive EA Energy is required when an electron is forced in the neutral atom (unstable ion formed) (addition of the electron is endothermic) 32

ELECTRON AFFINITY TRENDS Zeff increases NONMETALS HIGH ELECTRON AFFINITY (Atoms gain electrons easily) 33

VARIATIONS IN ELECTRON AFFINITIES I. Effect caused by Interelectron repulsions between outer shell electrons IVA VA VIA VIIA Expected Trend of EA Period 2 C N O F EA Should Period 3 Si P S Cl increase IVA VA VIA VIIA Actual Trend of EA Period 2 C N O F EA EA (kj/mol) 122 0 141 328 increases Period 3 Si P S Cl EA (kj/mol) 134 72 200 349 Reason: Atoms of Period 2 elements are much, much smaller than the atoms of Period 3 elements (large energy gap between the 2 nd and the 3 rd energy levels; this energy gap diminishes as one moves to 4 th, 5 th, 6 th, 7 th energy levels) In small atoms there is very strong inter electron electron repulsion (electrons are crowded). The mutual repulsions between 2 nd shell electrons act against adding an additional electron to the atom. Crowded Strong inter electron Period 2 Smaller electrons Repulsions Elements Atoms in outer shell between (2 nd shell) 2 nd shell electrons Less crowding Weaker inter electron Period 3 Larger of electrons Repulsions Elements Atoms in outer shell between (3 nd shell) 3 nd shell electrons 34

II. Effect caused by the stability of half filled subshells IIIA IVA VA VIA VIIA Period 2 B C N O F Period 3 Al Si P S Cl Expected trend of EA EA should increase IIIA IVA VA VIA VIIA Period 2 B C N O F E.A. (kj/mol) 27 122 0 141 328 Period 3 Al Si P S Cl E.A. (kj/mol) 44 134 72 200 349 E.A. increases E.A. increases Reason: Break in trend! E.A is less than expected! The more stable half filled shell of group VA elements rejects electrons, leading to a lower EA. IVA VA Period 2 Period 3 C [He]. 2s 2p Si [He]. 3s 3p N [He]. 2s 2p P [He]. 3s 3p 35

SUMMARY OF TRENDS IN PERIODIC PROPERTIES NONMETALS (SMALL ATOMS) HIGH IONIZATION ENERGY (difficult to remove electrons) HIGH ELECTRON AFFINITY (high tendency to gain electrons) METALS (LARGE ATOMS) LOW IONIZATION ENERGY (easy to remove electrons) LOW ELECTRON AFFINITY (difficult to gain electrons) 36

METALLIC CHARACTER The physical and chemical properties of the main group elements clearly display periodic character. The classification of elements in the periodic table into metals, non metals and metalloids is based on fundamental periodic trends. The more an element exhibits the physical and chemical properties of metals, the greater its metallic character. Metallic character increases The basic acidic behavior of the oxides of elements is a good indicator of their metallic character. Oxides are classified as basic or acidic based on their reactions with acids and bases. A basic oxide is an oxide that reacts with acids. Most metal oxides are basic. An acidic oxide is an oxide that reacts with bases. Most non metal oxides are acidic oxides. An amphoteric oxide is an oxide that has both basic and acidic properties. 37